Pyridylcarbonyl and thiocarbonyl derivatives useful as fungicides

ABSTRACT

The substituted heteroaryl compounds of this invention are good fungicides. In particular, they possess especially good activity against Bean Powdery Mildew, and other plant fungal diseases.

BACKGROUND OF THE INVENTION

This invention is drawn to novel fungicides.

With the world more dependent for food on an ever decreasing amount ofcultivated farmland, it is increasingly important to develop effectivefungicides which protect crops from fungicidal destruction.

Kozlik et al, in CA 79:53324Z, disclosed 1-carbamolyimidazoles asinsecticidal.

Brookes et al, in U.S. Pat. Nos. 4,080,462 and 3,991,071, disclosed1-(N,N-disubstituted carbamoyl and thiocarbamoyl)-imidazoles asfungicidal.

SUMMARY OF THE INVENTION

The compounds of the present invention are represented by the formula:##STR1## wherein R is phenyl, or phenyl substituted with 1 to 3substituents independently selected from fluoro, chloro, bromo, iodo,nitro, lower alkyl, lower alkoxy, lower alkyl or lower alkoxysubstituted with 1 to 3 of the same or different halogens; R¹ is loweralkyl, or --CH₂ Y wherein Y is lower alkenyl, lower alkenyl substitutedwith 1 to 3 of the same or different halogens, lower alkynyl, loweralkynyl substituted with 1 to 3 of the same or different halogens, loweralkoxyalkyl, lower alkoxy, lower alkyl-thioalkyl, lower thioalkyl, lowerhydroxyalkyl, lower haloalkyl, or halogen; R² is a 6-member heterocyclicring containing 1 to 2 nitrogen atoms and the remainder carbon atoms, a6-member heterocyclic ring containing 1 to 2 nitrogen atoms and theremainder carbon atoms with the ring substituted with 1 to 2 independentlower alkyl groups, a 5-member heterocyclic ring containing 1 to 2nitrogen atoms and the remainder carbon atoms, or a 5-memberheterocyclic ring containing 1 to 2 nitrogen atoms and the remaindercarbon atoms with the ring substituted with 1 to 2 independent loweralkyl groups, with the proviso that a nitrogen of the 5- or 6-memberheterocyclic ring is not bonded to the ##STR2## group; R³ is hydrogen orlower alkyl; Z is sulfur, or oxygen; and alk is a branched- orstraight-chain alkylene group of 1 to 10 carbons with the proviso thatthe chain length is no longer than 5 carbons.

Among other factors, the present invention is based on my finding thatthe compounds of this invention are effective fungicides. In particular,some of the compounds of this invention possess good activity againstBean Powdery Mildew.

In part due to their superior fungicidal activity, preferred R groupsinclude the trihalophenyl and dihalophenyl groups. Particularlypreferred R groups are 2,4,6-trihalophenyl and 2,6-dihalophenyl.

Preferred halogens include bromo and chloro.

Preferred R¹ groups include, for instance, lower hydroxyalkyl, loweralkyl and lower alkenyl groups. A particularly preferred R¹ group islower alkyl. Most preferably R¹ is ethyl or n-propyl.

Preferred R² groups include, for instance, 3-pyridyl, 5-pyrimidyl,2-pyrazyl and 5-(1-methylimidazolyl).

Preferred alk groups include, for instance, methylene, ethylene,propylene, 1-methylethylene, and the like. Most preferably, alk isethylene.

DEFINITIONS

As used herein, the following terms have the following meanings, unlessexpressly stated to the contrary.

The term "alkenyl" refers to unsaturated alkyl groups having a doublebond [e.g., CH₃ CH═CH(CH₂)₂ --,] and includes both straight- andbranched-chain alkenyl groups.

"Lower alkenyl" groups refer to alkenyl groups having from 2 through 6carbon atoms. Typical lower alkenyl groups include, for example,ethylene, but-3-enyl, hex-4-enyl, 2-methylpent-4-enyl, and the like.

The term "alkynyl" refers to unsaturated alkyl groups having a triplebond [e.g., CH₃ .tbd.C(CH₂)₂ --] and includes both straight- andbranched-chain alkynyl groups.

The term "lower alkynyl" refers to alkynyl groups having from 2 through6 carbon atoms and includes, for example, but-3-ynyl, hex-4-ynyl,3-methylpent-4-ynyl, and the like.

The term "alkyl" refers to both straight- and branched-chain alkylgroups. Generally, such alkyl groups contain from 1 through 12 carbonatoms.

The term "lower alkyl" refers to both straight- and branched-chain alkylgroups having a total from 1 through 6 carbon atoms and includesprimary, secondary and tertiary alkyl groups. Typical lower alkylsinclude, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl,t-butyl, n-hexyl, and the like.

The term "halo" or "halogen atom" refers to the groups fluoro, chloro,bromo and iodo.

The term "alkoxy" refers to the group R'O-- wherein R' is alkyl.

The term "lower alkoxy" refers to the alkoxy groups having from 1through 6 carbon atoms and includes, for example, methoxy, ethoxy,t-butoxy, hexoxy, and the like.

The term "lower alkoxyalkyl" refers to groups having the formulaR"OR'"-- wherein R" and R'" are independently lower alkyl. Typical loweralkoxyalkyl groups include, for instance, methoxymethyl, methoxypropyl,isopropoxybutyl, hexoxyhexyl, and the like.

The term "lower hydroxyalkyl" refers to the group HOR"-- wherein R" islower alkyl. Such groups include, for example, hydroxymethyl,hydroxyethyl, hydroxyhexyl, and the like.

The term "thioalkyl" refers to the group having the formula R'S--wherein R' is alkyl.

The term "lower thioalkyl" refers to such alkylthio groups wherein thealkyl groups is a lower alkyl. Typical lower alkyl groups include, forexample, methylthio, ethylthio, t-butylthio, and the like.

The term "lower alkylthioalkyl" refers to the group R"SR'"-- wherein R"and R'" are independently lower alkyl. Typical lower alkylthioalkylgroups include, for instance, methylthiomethyl (e.g., CH₃ SCH₂ --),ethylthiomethyl (e.g., CH₃ CH₂ SCH₂ --), and the like.

The term "haloalkyl" refers to alkyl groups having one or more halosubstituents. Typical haloalkyl groups include, for example,trifluoromethyl, dichloromethyl, bromochloromethyl, 1,2-dibromoethyl,3-iodopropyl, chloromethyl, and the like.

The term "a 6-member heterocyclic ring containing 1 to 2 nitrogens"refers to the groups pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, and thelike.

The term "a 5-member heterocyclic ring containing 1 to 2 nitrogens"refers to the groups imidazolyl, pyrrolyl, pyrazolyl and the like.

The term "alk" refers to straight- and branched-chain alkylene groups of1 to 10 carbons and includes, for instance, ethylene, propylene,2-methylpropylene ##STR3## 3-methylpentylene ##STR4## and the like.

The term "ethylenediamine" refers to the group H₂ NCH₂ CH₂ NH₂.

The term "N'-(n-propyl), N'-(3-pyridylcarbonyl) ethylenediamine" refersto the group: ##STR5##

The term "N-(2,4,6-trichlorophenyl)-N'-(n-propyl),N'-(3-pyridylcarbonyl) ethylenediamine refers to the group: ##STR6##

The term "nicotine amide" refers to the group: ##STR7##

The term "pyrazinamide" refers to the group: ##STR8##

DETAILED DESCRIPTION OF THE INVENTION

The compounds of this invention are prepared according to the followingsynthetic scheme: ##STR9## wherein R, R¹, R², R³, and alk are as definedabove; W and W' are independently halogen, b is a base, b₂ is an acidscavenger (base), and A is a straight- or branched-chain alkylene group1 carbon shorter in length than the resulting alk group.

Reaction (1) is conducted by adding an essentially equimolar amount of ahaloalkyl acid halide, III, to II. The reaction is conducted in theliquid phase employing an aprotic anhydrous organic solvent such aschloroform, methylene chloride, toluene, and the like. An essentiallyequimolar amount of a base, IV, is added to the system to scavenge theacid generated during the reaction. Preferably, an organic base such asa trialkylamine (e.g., triethylamine), pyridine, and the like isemployed. Reaction pressure is not critical and for convenience, thereaction is conducted at atmospheric pressure. The reaction is generallyconducted at from -20° C. to 80° C., although preferably at from 0° C.to 25° C., and is generally complete from within 1 to 24 hours. Theresulting amide, V, is then isolated by conventional procedures such asextraction, filtration, chromatography, distillation, or alternatively,is used in Reaction (2) without purification and/or isolation.

Reaction (2) is conducted by adding an essentially equimolar amount ofthe appropriate primary amine, VI, to V. An essentially equimolar amountof a base, IV, is added to the system in order to scavenge the acidgenerated during the reaction. Preferably, an organic base such as atrialkylamine (e.g., triethylamine), pyridine, and the like is employed.The reaction is done in the liquid phase using an inert anhydrousorganic solvent such as chloroform, methylene chloride, dimethoxyethane,and the like. Alternatively, in lieu of adding solvent and base, thereaction may be accomplished by using an excess of primary amine.Reaction pressure is not critical and for convenience, the reaction isgenerally conducted at atmospheric pressure. The reaction is generallyconducted at from 0° C. to 100° C., although preferably at from 20° C.to 50° C., and is generally complete from within 1 to 24 hours. Theproduct, VII, is isolated by conventional procedures such as extraction,filtration, chromatography, distillation, or alternatively, used inReaction (3) without isolation and/or purification.

Reaction (3) is a conventional reduction of the amide to the amine.

In preparing compounds of this invention wherein the carbonyl of theamide is reduced to the methylene group, the reaction is convenientlyconducted by adding an essentially equimolar amount of a reducing agent,Rd, to VIII. The reaction is conducted in the liquid phase employing aninert anhydrous organic solvent such as toluene, benzene, and the like.Suitable reducing agents include, for instance, lithium aluminumhydride, borane, borane methyl sulfide, and the like. Preferably, due tothe ease in handling the reagent, borane methyl sulfide is employed asthe reducing agent. However, when R¹ is a group susceptible to anundesired reaction with borane or borane methyl sulfide (such as allyl,propargyl, and the like), the preferred reducing agent is lithiumaluminum hydride. Reaction pressure is not critical and for convenience,the reaction is conducted at atmospheric pressure. The reaction isgenerally conducted at from 0° C. to 110° C., although preferably atfrom 30° C. to 70° C., and is generally complete from within 1 to 24hours. The resulting amine, IX, is isolated by conventional proceduressuch as extraction, filtration, chromatography, distillation, oralternatively, used in Reaction (4) without purification and/orisolation.

Reaction (4) is conducted by first preparing reagent X. X is prepared byadding an essentially equimolar amount of carbonyldiimidazole to theappropriate acid, R² CO₂ H wherein R² is as defined above. The reactionis conducted in the liquid phase using an inert anhydrous organicsolvent such as chloroform, methylene chloride, dimethoxyethane,toluene, and the like. Reaction pressure is not critical and forconvenience, the reaction is generally conducted at atmosphericpressure. The reaction is generally conducted at from 0° C. to 100° C.,although preferably at room temperature, and is generally complete fromwithin 1 to 24 hours. The resulting reagent, X, may be isolated byconventional procedures such as extraction, filtration, chromatography,distillation, and the like. Alternatively and preferably, the reagent isnot isolated from the reaction solution but an essentially equimolaramount of the amine, IX, is added to the system. Reaction pressure forthis reaction is not critical and for convenience, the reaction isgenerally conducted at atmospheric pressure. After addition of IX, thereaction is generally conducted at room temperature and is generallycomplete from within 1 to 24 hours. The product, Ia, is then isolated byconventional procedures such as extraction, filtration, chromatography,distillation, or alternatively, used in Reaction (5) withoutpurification and/or isolation.

Alternatively, product Ia may be prepared by Reaction (4a) using theacid chloride XI corresponding to R² CO₂ H. Acid chloride XI may beconveniently prepared by combining approximately equimolar amounts of R²CO₂ H and thionyl chloride. The reaction is conducted in the liquidphase using an inert organic solvent such as methylene chloride,toluene, chloroform, and the like. It is preferred to conduct thereaction in the presence of a catalytic amount of dimethylformamide. Thereaction mixture is heated to reflux and refluxed for about 0 to about24 hours. The mixture is stirred until gas evolution ceases. After thetemperature of the mixture returns to room temperature, XI may be usedin Reaction (4a) without purification or isolation. Since XI issusceptible to hydrolysis, minimal handling of it is preferred.

Reaction (4a) is conducted by combining XI, with IX and IVa. Thereaction is conducted in the liquid phase using an inert organic solventsuch as methylene chloride, chloroform, toluene, and the like. Suitableacid scavengers, b₂ (IVa), include bases such as triethylamine,pyridine, an alkyl amine, sodium carbonate, and the like. The reactionis carried out at a temperature of about -25° C. to about 100° C.,preferably from about 0° C. to about 25° C., and may be convenientlycarried out at room temperature. The reaction is generally completewithin about 0 to about 24 hours. Product Ia is then isolated byconventional procedures such as extraction, filtration, chromatography,distillation, or alternatively, used in Reaction (5) withoutpurification and/or isolation.

Reaction (5) is conducted by adding an essentially equimolar amount ofphosphorus pentasulfide, XII, to Ia. The reaction is conducted in theliquid phase using an inert anhydrous organic solvent such as toluene,tetrahydrofuran, and the like. Preferably, the system is exposed tomicrowave radiation in order to facilitate the dispersion of phosphoruspentasulfide into solution. Reaction pressure is not critical and forconvenience, the reaction is generally conducted at atmosphericpressure. The reaction is generally conducted at from 15° C. to 100° C.,althouth preferably it is conducted at the ambient temperature and isgenerally complete from within 1 to 48 hours. The product Ib is thenisolated by conventional procedures such as extraction, filtration,chromatography, distillation, and the like.

UTILITY

The compounds of the invention are effective in controlling fungalinfections. Some of the compounds of this invention are particularlyeffective in controlling powdery mildew fungal infections caused by theorganism Erysiphe polygoni. Some of the compounds of this invention arealso useful for controlling leaf blights caused by organisms such asPhytophthora infestans conidia, Alternaria solani conidia, and Septoriaapii. Some of the compounds of this invention are also useful forcontrolling fungal infections caused by Uromyces phaseoli tipica,Plasmopara viticola, and Piricularia oryzae. However, some fungicidalcompounds of this invention may be more fungicidally active than othersagainst particular fungi.

When used as fungicides, the compounds of the invention are applied infungicidally effective amounts to fungi and/or their habitats, such asvegetative hosts and non-vegetative hosts, e.g., animal products. Theamount used will, of course, depend on several factors such as the host,the type of fungus, and the particular compound of the invention. Aswith most pesticidal compounds, the fungicides of the invention are notusually applied full strength, but are generally incorporated withconventional, biologically inert extenders or carriers normally employedfor facilitating dispersion of active fungicidal compounds, recognizingthat the formulation and mode of application may affect the activity ofthe fungicide. Thus, the fungicides of the invention may be formulatedand applied as granules, as powdery dusts, as wettable powders, asemulsifiable concentrates, as solutions, or as any of several otherknown types of formulations, depending on the desired mode ofapplication.

Wettable powders are in the form of finely divided particles whichdisperse readily in water or other dispersants. These compositionsnormally contain from about 5% to 80% fungicide, and the rest inertmaterial, which includes dispersing agents, emulsifying agents andwetting agents. The powder may be applied to the soil as a dry dust, orpreferably as a suspension in water. Typical carriers include fuller'searth, kaolin clays, silicas, and other highly absorbent, readilywettable, inorganic diluents. Typical wetting, dispersing or emulsifyingagents include, for example: the aryl and alkylaryl sulfonates and theirsodium salts; alkylamide sulfonates, including fatty methyl taurides;alkylaryl polyether alcohols, sulfated higher alcohols and polyvinylalcohols; polyethylene oxides; sulfonated animal and vegetable oils;sulfonated petroleum oils; fatty acid esters of polyhydric alcohols andthe ethylene oxide addition products of such esters; and the additionproducts of long-chain mercaptans and ethylene oxide. Many other typesof useful surface-active agents are available in commerce. Thesurface-active agent, when used, normally comprises from 1% to 15% byweight of the fungicidal composition.

Dusts are freely flowing admixtures of the active fungicide with finelydivided solids such as talc, natural clays, kieselguhr, pyrophyllite,chalk, diatomaceous earths, calcium phosphates, calcium and magnesiumcarbonates, sulfur, lime, flours, and other organic and inorganic solidswhich act as dispersants and carriers for the toxicant. These finelydivided solids have an average particle size of less than about 50microns. A typical dust formulation useful herein contains 75% silicaand 25% of toxicant.

Useful liquid concentrates include the emulsifiable concentrates, whichare homogeneous liquid or paste compositions which are readily dispersedin water or other dispersant, and may consist entirely of the fungicidewith a liquid or solid emulsifying agent, or may also contain a liquidcarrier such as xylene, heavy aromatic naphthas, isophorone, and othernonvolatile organic solvents. For application, these concentrates aredispersed in water or other liquid carrier, and are normally applied asa spray to the area to be treated.

Other useful formulations for fungicidal applications include simplesolutions of the active fungicide in a dispersant in which it iscompletely soluble at the desired concentration, such as acetone,alkylated naphthalenes, xylene, or other organic solvents. Granularformulations, wherein the fungicide is carried on relatively coarseparticles, are of particular utility for aerial distribution or forpenetration of cover-crop canopy. Pressurized sprays, typically aerosolswherein the active ingredient is dispersed in finely divided form as aresult of vaporization of a low-boiling dispersant solvent carrier, suchas the Freons, may also be used. All of those techniques for formulatingand applying fungicides are well known in the art.

The percentages by weight of the fungicide may vary according to themanner in which the composition is to be applied and the particular typeof formulation, but in general comprise 0.5% to 95% of the toxicant byweight of the fungicidal composition.

The fungicidal compositions may be formulated and applied with otheractive ingredients, including other fungicides, insecticides,nematocides, bactericides, plant-growth regulators, fertilizers, etc.

A further understanding of the invention can be had in the followingnon-limiting Examples. Wherein, unless expressly stated to the contrary,all temperature ranges refer to the Centigrade system and the term"ambient" or "room temperature" refers to about 20° C. to 25° C. Theterm "percent" refers to gram moles. The term "equivalent" refers to aquantity of reagent equal in moles, to the moles of the preceding orsucceeding reagent recited in that example in terms of finite moles orfinite weight or volume. Also, unless expressly stated to the contrary,geometric isomer and racemic mixtures are used as starting materials andcorrespondingly, isomer mixtures are obtained as products.

Compounds which were prepared in accordance with Examples 1 through 4below are found in Table I.

EXAMPLES Example 1 Preparation ofα-bromo-(2',4',6'-trichlorophenyl)acetamide

2,4,6-trichloroaniline, 49.1 gm, was added to 250 ml of methylenechloride. The solution was cooled to 0° C. to 5° C. After cooling, 34.8gm of triethylamine was added to the system. Then 21.8 ml of bromoacetylbromide was added and the system allowed to warm to room temperature.The system was stirred at room temperature for 18 hours. The reactionwas then stopped and the methylene chloride solution was washed withsaturated sodium bicarbonate solution. The methylene chloride layer wasseparated and partially stripped when a solid precipitated. The solidwas filtered and air dried to yield 41.4 gm of theα-bromo-(2',4',6'-trichlorophenyl)acetamide as a gray solid.

Example 2 Preparation ofN-(2,4,6-trichlorophenyl)-N'-(n-propyl)glycinamide

α-bromo-(2',4',6'-trichlorophenyl)acetamide, 41.4 gm, was added to 100ml of n-propylamine. The system was heated overnight at reflux. Theexcess n-propylamine was then stripped. The residue was dissolved inmethylene chloride and washed with water. The solid precipitate(unreacted acetanilide) was filtered. The methylene chloride solutionwas removed by stripping to give 15.1 gm ofN-(2,4,6-trichlorophenyl)-N'-(n-propyl)glycinamide.

Example 3 Preparation ofN-(2,4,6-trichlorophenyl)-N'-(n-propyl)ethylenediamine

N-(2,4,6-trichlorophenyl)-N'-(n-propyl)glycinamide, 28.7 gm, was addedto 150 ml of toluene. 18.4 ml of borane methyl sulfide (2 equivalents)was then slowly added to the system. The system was heated atapproximately 60° C. for 48 hours at which time reaction completion waschecked by IR spectroscopy. 100 ml of methanol was then slowly added tothe system. After addition of the methanol, the system was acidified bybubbling in HCl gas. Afterwards, the system was refluxed for 1 hour. Thesolvent was then removed by stripping. The resulting oil as dissolved inmethanol which was then stripped. The oil was next dissolved inmethylene chloride. The organic solution was washed with a sodiumhydroxide solution and then with water. The methylene chloride wasremoved by stripping to give 17.5 gm of theN-(2,4,6-trichlorophenyl)-N'-(n-propyl)ethylenediamine as an amber oil.

Example 4 Preparation of N-(2,4,6-trichlorophenyl)-N'-(n-propyl),N'-(3-pyridylcarbonyl)ethylenediamine

(a) 3-pyridine carboxylic acid, 5.0 gm, was added to 15 ml of methylenechloride. 6.4 gm of carbonyldiimidazole was added to the system. Thesystem was stirred at room temperature for 16 hours to give the3-pyridyl carboxylic acid imidazolide.

(b) N-(2,4,6-trichlorophenyl)-N'-(n-propyl)ethylenediamine, 5.6 gm, wasthen added to the system. The system was stirred at room temperature for24 hours. The reaction was then stopped and the methylene chloridesolution was washed with a sodium bicarbonate solution and then withwater. The methylene chloride solution was dried over magnesium sulfateand the methylene chloride removed by stripping to give 2.55 gm ofN-(2,4,6-trichlorophenyl)-N'-(n-propyl),N'-(3-pyridylcarbonyl)ethylenediamine as a reddish brown oil and listedas Compound No. 1, Table I.

By following the procedures of Examples 1 to 4 and using the appropriatestarting materials and reagents, the following compounds are prepared:

N-(2,4,6-trichlorophenyl)-N'-(n-propyl),N'-(2-pyrazinylcarbonyl)ethylenediamine;

N-(2,4,6-trichlorophenyl)-N'-(n-propyl),N'-(3-pyridylcarbonyl)ethylenediamine;

N-(2,4,6-tribromophenyl)-N'-(n-propyl),N'-(5-pyrimidylcarbonyl)ethylenediamine;

N-(2,4,6-trichlorophenyl)-N'-(n-propyl),N'-(1-methyl-5-imidazolylcarbonyl)ethylenediamine;

N-(4-t-butylphenyl)-N'-(n-propyl),N'-(5-pyrimidylcarbonyl)ethylenediamine;

N-(2,4,6-trichlorophenyl)-N'-allyl,N'-(3-pyridylcarbonyl)ethylenediamine;

N-(4,6-dichlorophenyl)-N'-(2-chloroallyl),N'-(3-pyridylcarbonyl)ethylenediamine;

N-(4-t-butylphenyl)-N'-(2-bromoallyl),N'-(5-pyrimidylcarbonyl)ethylenediamine;

N-(2,4,6-trichlorophenyl)-N'-(methoxyethyl),N'-(3-pyridylcarbonyl)ethylenediamine;

N-(2,4,6-tribromophenyl)-N'-(ethoxyethyl),N'-(1-methyl-5-imidazolylcarbonyl)ethylenediamine;

N-(2,4,6-triidophenyl)-N'-(ethoxyethyl),N'-(1-methyl-5-imidazolylcarbonyl)ethylenediamine;

N-(2,4,6-trichlorophenyl)-N'-(methylthioethyl),N'-(3-pyridylcarbonyl)ethylenediamine;

N-(4-t-butylphenylether)-N'-(propargyl),N'-(3-pyridylcarbonyl)ethylenediamine;

N-phenyl-N'-chloromethyl, N'-(5-pyrimidylcarbonyl)ethylenediamine;

N-(4-methylphenyl)-N'-bromomethyl,N'-(2-pyrazinylcarbonyl)ethylenediamine;

N-(4-ethylphenyl)-N'-(2,2,2-trichloroethyl),N'-(3-pyridylcarbonyl)ethylenediamine;

N-(2,6-dimethylphenyl)-N'-(ethylthioethyl),N'-(3-pyridylcarbonyl)ethylenediamine;

N-phenyl-N'-(2-hydroxyethyl),N'-(1-methyl-5-imidazolylcarbonyl)ethylenediamine;

N-(2,4,6-trichlorophenyl)-N'-(n-propyl),N'-(3-pyridylcarbonyl)propylenediamine;

N-(2,4,6-trichlorophenyl)-N'-(n-propyl),N'-(3-pyridylcarbonyl)2-methylpropylenediamine;

N-(2,4,6-trichlorophenyl)-N'-(n-propyl),N'-(3-pyridylcarbonyl)butylenediamine;

N-(2,4,6-trichlorophenyl)-N'-(n-propyl),N'-(3-pyridylcarbonyl)2,2-dimethylpropylenediamine;

N-(2,4,6-trichlorophenyl)-N'-(n-propyl),N'-(3-pyridylcarbonyl)2-ethylpropylenediamine;

N-(2,4,6-trichlorophenyl)-N'-allyl,N'-(2-pyrazinylcarbonyl)2,3-dimethylbutylenediamine;

N-(2,4,6-trichlorophenyl)-N-(n-propyl)-N'-(3-pyridylthiocarbonyl)ethylenediamine;

N-(4-t-butylphenyl)-N'-(2-pyrazinylthiocarbonyl),N'-(n-propyl)ethylenediamine;

N-(2,4,6-trimethylphenyl)-N'-(2-chloroethyl)-N'-(5-pyrimidylthiocarbonyl)ethylenediamine;and

N-(4-trifluoromethylphenyl)-N'-(n-propyl)-N'-(3-pyridylcarbonyl)ethylenediamine.

EXAMPLE A Bean Powdery Mildew

The compounds of the invention were tested for the control of the BeanPowdery Mildew organism Erysiphe polygoni. Seedling bean plants weresprayed with a 250-ppm solution of the test compound in acetone, waterand a nonionic emulsifier. The sprayed plants were then inoculated 1 daylater with the organism. The plants were maintained for 10 days attemperatures of 68° F. at night with daytime temperatures of 72° F. to80° F.; relative humidity was maintained at 40% to 60%. The percentdisease control provided by a given test compound was based on thepercent disease reduction relative to the untreated check plants. Theresults are tabulated in Table II.

EXAMPLE B Tomato Late Blight

Compounds of the invention were tested for the preventative control ofthe Tomato Late Blight organism Phytophthora infestans. Five- tosix-week-old tomato (cultivar Bonny Best) seedlings were used. Thetomato plants were sprayed with a 250-ppm suspension of the testcompound in acetone, water and a nonionic emulsifier. The sprayed plantswere then inoculated 1 day later with the organism, placed in anenvironmental chamber and incubated at 66° F. to 68° F. and 100%relative humidity for at least 16 hours. Following the incubation, theplants were maintained in a greenhouse for approximately 7 days. Thepercent disease control provided by a given test compound was based onthe percent disease reduction relative to untreated check plants. Theresults are tabulated in Table II.

EXAMPLE C Celery Late Blight

The Celery Late Blight tests were conducted using celery (Utah) plants11 weeks old. The Celery Late Blight organism was Septoria apii. Thecelery plants were sprayed with 250-ppm solutions of the candidatetoxicant mixed with acetone, water and a nonionic emulsifier. The plantswere then inoculated with the organism and placed in an environmentalchamber and incubated at 66° F. to 68° F. in 100% relative humidity foran extended period of time (approximately 48 hours). Following theincubation, the plants were allowed to dry and then were maintained in agreenhouse for approximately 14 days. The percent disease controlprovided by a given candidate toxicant is based on the percent diseasereduction relative to untreated check plants. The results are reportedin Table II.

EXAMPLE D Tomato Early Blight

Compounds of the invention were tested for the control of the TomatoEarly Blight organism Alternaria solani conidia. Tomato (variety BonnyBest) seedlings of 6- to 7-weeks old were used. The tomato plants weresprayed with a 250-ppm solution of the test compound in anacetone-and-water solution containing a small amount of a nonionicemulsifier. The sprayed plants were inoculated 1 day later with theorganism, placed in the environmental chamber and incubated at 66° F. to68° F. and 100% relative humidity for 24 hours. Following theincubation, the plants were maintained in a greenhouse for about 12days. Percent disease control was based on the percent diseasedevelopment on untreated check plants. The compounds tested and theresults are tabulated in Table II.

EXAMPLE E Grape Downy Mildew

The compounds of the invention were tested for the control of the GrapyDowny Mildew organism PLasmopara viticola. Detached leaves, between 70mm and 85 mm in diameter, 7-week-old Vitis vinifera cultivar Emperorgrape seedlings were used as hosts. The leaves were sprayed with a250-ppm solution of the test compound in acetone. The sprayed leaveswere dried, inoculated with a spore suspension of the organism, placedin a humid environmental chamber and incubated at 66° F. to 68° F. andabout 100% relative humidity. After incubation for 2 days, the plantswere then held in a greenhouse 7 to 9 days; then the amount of diseasecontrol was determined. The percent disease control provided by a giventest compound was based on the percent disease reduction relative tountreated check plants. The results are tabulated in Table II.

EXAMPLE F Leaf Rust

The Leaf Rust test was made using pinto beans. The pathogen was Uromycesphaseoli tipica. The pinto bean plants were sprayed with a 250-ppmsolution of the test compound in an acetone-water mixture containing anonionic emulsifier. The treated plants were inoculated thereafter withthe pathogen and then incubated in an environmental chamber forapproximately 20 hours at 100% relative humidity and a temperature of68° F. to 70° F. The plants were then removed from the chamber, allowedto dry, and then maintained in a greenhouse at a 60% to 80% relativehumidity. The rate of infection on the leaves was made after about 14days. The percent disease control provided by a given test compound wasbased on the percent disease reduction relative to untreated checkplants. The results are reported in Table II.

EXAMPLE G Rice Blast

Compounds of this invention were tested for control of the Rice Blastorganism Piricularia oryzae, using 10- to 14-day-old rice plantseedlings (Calrose M-9 variety). Seedling plants were sprayed with a625-ppm solution of the test compound in acetone, water and a nonionicemulsifier (ORTHO X-77 spreader). The sprayed plants were inoculated 1day later with the organism in an environmental chamber. Afterinoculation, the plants were kept in an environmental chamber for about48 hours under conditions of about 72° F. to 75° F. and about 100%relative humidity. Following the incubation period, the plants wereplaced in a greenhouse with a temperature of about 72° F. and maintainedwith bottom watering for about 12 to 16 days. The percent diseasecontrol provided by a given test compound is based on a comparison ofthe percentage disease relative to the percent disease development onthe untreated check plants: ##EQU1## The results are tabulated in TableII.

                                      TABLE I    __________________________________________________________________________    Compounds Of The Formula:     ##STR10##                                 ANALYSIS    Compound                     Carbon  Hydrogen                                                 Nitrogen    No.   Z  X  R         R.sup.2                                 Calc.                                     Found                                         Calc.                                             Found                                                 Calc.                                                     Found                                                         Form  m.p.    __________________________________________________________________________    1     O  NH                 ##STR11##                           ##STR12##                                 52.79                                     51.88                                         4.69                                             4.83                                                 10.86                                                     10.52                                                         oil   75°-    2     O  NH                 ##STR13##                           ##STR14##                                 49.56                                     49.42                                         4.42                                             4.45                                                 14.45                                                     14.95                                                         white                                                               77°    __________________________________________________________________________                                                               C.

                  TABLE II    ______________________________________    Fungicidal Activity    Compound            Control    No.     GDM     TLB    CLB   TEB   BR   BPM   RB    ______________________________________    1        0      0      29    27    0    56     0    2       31      0      29     0    0     0    38    ______________________________________     GDM  Grape Downy Mildew (Plasmopara viticola)     TLB  Tomato Late Blight (Phytophthora infestans)     CLB  Celery Late Blight (Septoria apii)     TEB  Tomato Early Blight (Alternaria solani conidia)     BR  Bean Rust (Uromyces phaseoli tipica)     BPM  Bean Powdery Mildew (Erysiphe polygoni)     RB  Rice Blast (Piricularia oryzae)

What is claimed is:
 1. A compound of the formula: ##STR15## wherein R isphenyl, or phenyl substituted with 1 to 3 substituents independentlyselected from fluoro, chloro, bromo, iodo, nitro, lower alkyl, loweralkoxy, lower alkyl or lower alkoxy substituted with 1 to 3 of the sameor different halogens; R¹ is lower alkyl, or --CH₂ Y wherein Y is loweralkenyl, lower alkenyl substituted with 1 to 3 of the same or differenthalogens, lower alkynyl, lower alkynyl substituted with 1 to 3 of thesame or different halogens, lower alkoxyalkyl, lower alkoxy, loweralkylthioalkyl, lower thioalkyl, lower hydroxyalkyl, lower haloalkyl, orhalogen; R² is pyridyl or pyridyl substituted with 1 to 2 independentlower alkyl groups, with the proviso that a nitrogen of the pyridyl ringis not bonded to the ##STR16## group; R³ is hydrogen or lower alkyl; Zis sulfur, or oxygen; and alk is both branched- and straight-chainalkylene groups of 1 to 10 carbons with the proviso that the chainlength is no longer than 5 carbons.
 2. A compound of the formula definedin claim 1 wherein R¹ is lower alkyl or CH₂ Y wherein Y is loweralkenyl, lower alkynyl, lower alkoxyalkyl, lower alkoxy, lowerhydroxyalkyl, lower haloalkyl or halogen.
 3. A compound of the formuladescribed in claim 2 wherein R¹ is lower alkyl.
 4. A compound of theformula defined in claim 3 wherein R¹ is propyl.
 5. A compound of theformula defined in claim 1 wherein R is phenyl substituted with 1 to 3substituents selected from fluoro, chloro, bromo, iodo, nitro, loweralkyl, lower alkoxy or lower alkyl substituted with 1 to 3 halogens. 6.A compound of the formula defined in claim 5 wherein R is phenylsubstituted with 1 to 3 halogens.
 7. A compound of the formula definedin claim 6 wherein R is 2,4,6-trihalophenyl.
 8. A compound of theformula defined in claim 7 wherein R is 2,4,6-trichlorophenyl.
 9. Acompound of the formula defined in claim 1 wherein R² is 3-pyridyl. 10.A compound of the formula defined in claim 9 wherein R is2,4,6-trichlorophenyl, R₁ is propyl, R₃ is hydrogen, Z is oxygen and alkis ethylene.
 11. A fungicidal composition comprising a biologicallyinert carrier and a fungicidally effective amount of a compound of theformula defined in claim
 1. 12. A fungicidal composition comprising abiologically inert carrier and a fungicidally effective amount of acompound of the formula defined in claim
 3. 13. A fungicidal compositioncomprising a biologically inert carrier and a fungicidally effectiveamount of a compound of the formula defined in claim
 10. 14. A methodfor controlling fungi comprising contacting said fungi or their growthenvironment with a fungicidally effective amount of a compound of theformula defined in claim
 1. 15. A method for controlling fungicomprising contacting said fungi or their growth environment with afungicidally effective amount of a compound of the formula defined inclaim
 3. 16. A method for controlling fungi comprising contacting saidfungi or their growth environment with a fungicidally effective amountof a compound of the formula defined in claim 10.